KR102046525B1 - Multilayer laser marking film and method for manufacturing the same - Google Patents

Abstract

Adhesive layer; A colored base layer having a first color; And a colored coating layer having a second color, wherein the first color and the second color are different colors from each other, and the colored coating layer includes a cured product of a coating composition including a photocurable oligomer, a thermosetting oligomer, and a pigment. The photocurable oligomer includes an epoxy (meth) acrylate oligomer, a urethane (meth) acrylate oligomer or a mixed oligomer thereof, and the thermosetting oligomer includes an isocyanate oligomer, and the colored coating layer has an uneven pattern on its surface. It provides a multi-layer laser marking film and a method for producing the same.

Description

Multilayer Laser Marking Film and Manufacturing Method Thereof {MULTILAYER LASER MARKING FILM AND METHOD FOR MANUFACTURING THE SAME}

The present invention relates to a multilayer laser marking film excellent in security, high adhesion, and capable of writing various information, and a method of manufacturing the same.

Various articles have labels for unique identification functions. These labels contain a variety of information about the item and may also perform unique identification functions. Labels used in the automotive industry, for example, may be used to display information about various parts of a vehicle, such as tire pressure or fuel type, or to display unique security information such as, for example, chassis number and vehicle identification number. It is used. In case of theft or accident, these labels allow tracking of the vehicle.

As one kind of method of manufacturing such a label, a method of writing information with a laser is used. Lasers are easy to be used for machining as high power light sources. For example, Korean Patent Publication No. 10-2006-0027501 includes an adhesive label sheet capable of marking a large amount of barcodes in a short time using a laser. Japanese Laid-Open Patent Publication No. 1990-120042 discloses a heat resistant display material having a marked layer having an etching pattern formed by a laser beam on a heat resistant base layer.

Such a label should have physical properties that can be precisely processed by a laser, have excellent adhesion to adherends, and simultaneously implement various physical properties corresponding to a purpose and purpose. Therefore, there is a need for a study to control the properties of the label according to each use and purpose.

One embodiment of the present invention includes a fine and various characters, patterns, etc. through the uneven pattern of the surface, and can be precisely processed by laser marking, when applied to the actual product without being damaged during the evaluation of physical properties Provided is a multilayer laser marking film that exhibits fracture properties for counterfeiting and modulation attempts.

Another embodiment of the present invention is a method of manufacturing the multi-layer laser marking film it can be produced through the multi-layer laser marking film having excellent physical properties.

In one embodiment of the invention, the adhesive layer; A colored base layer having a first color; And a colored coating layer having a second color, wherein the first color and the second color are different colors from each other, and the colored coating layer includes a cured product of a coating composition including a photocurable oligomer, a thermosetting oligomer, and a pigment. The photocurable oligomer includes an epoxy (meth) acrylate oligomer, a urethane (meth) acrylate oligomer or a mixed oligomer thereof, and the thermosetting oligomer includes an isocyanate oligomer, and the colored coating layer has an uneven pattern on its surface. It provides a multilayer laser marking film comprising.

In another embodiment of the invention, the step of applying a substrate composition on top of one release film, and laminating another release film thereon; Curing the substrate composition to prepare a laminate having a colored substrate layer having a first color disposed between two release films; After removing one release film from the laminate, a coating composition including a photocurable oligomer, a thermosetting oligomer and a pigment is applied to one surface of the colored substrate layer, and a printing method is performed such that an uneven pattern is formed on the surface of the coating composition. Applying; Forming a colored coating layer having a second color different from the first color by first and second photocuring the coating composition having the uneven pattern formed thereon; And removing the other release film from the laminate and forming an adhesive layer on the back surface of the colored substrate layer.

The multi-layer laser marking film may include fine and various characters, patterns, etc. through its uneven pattern on the surface, and can be precisely processed by laser marking, and applied to actual products without being damaged when evaluating physical properties. Provides a multi-layer laser marking film that exhibits fracture resistance to counterfeiting and tampering attempts, resulting in superior security.

Through the method of manufacturing the multilayer laser marking film, the multilayer laser marking film simultaneously exhibiting the above-described physical properties may be manufactured.

1 is a schematic cross-sectional view of a multilayer laser marking film according to an embodiment of the present invention.
FIG. 2 schematically illustrates a cross section when laser marking is performed on the multilayer laser marking film of FIG. 1.
3 is a schematic cross-sectional view of a multilayer laser marking film according to another embodiment of the present invention.
4 schematically illustrates a method of manufacturing a multilayer laser marking film according to an embodiment of the present invention.

Advantages and features of the present invention, and methods for achieving the same will be apparent with reference to the following embodiments. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various forms. The present embodiments are merely provided to make the disclosure of the present invention complete, and to fully convey the scope of the invention to those skilled in the art, and the present invention is defined by the scope of the claims. It will be. Like reference numerals refer to like elements throughout.

In the drawings, the thickness of layers, films, panels, regions, etc., are exaggerated for clarity. In the drawings, the thicknesses of layers and regions are exaggerated for clarity.

In addition, in this specification, when a part such as a layer, film, region, plate, or the like is said to be "on" or "upper" another part, it is not only when the other part is "right over" but also when there is another part in the middle. Also includes. On the contrary, when a part is "just above" another part, there is no other part in the middle. In addition, when a part such as a layer, a film, an area, or a plate is "below" or "below" another part, it is not only when another part is "below" but also another part in the middle. Include. In contrast, when a part is "just below" another part, there is no other part in the middle.

In one embodiment of the present invention, a multilayer laser marking film is provided. The multilayer laser marking film is an adhesive layer; A colored base layer having a first color; And a colored coating layer having a second color, wherein the first color and the second color are different colors from each other. In addition, the colored coating layer comprises a cured product of a coating composition comprising a photocurable oligomer, a thermosetting oligomer and a pigment, the photocurable oligomer is an epoxy (meth) acrylate oligomer, urethane (meth) acrylate oligomer or a mixture thereof An oligomer, wherein the thermosetting oligomer comprises an isocyanate-based oligomer. Further, the colored coating layer includes an uneven pattern on the surface.

1 schematically illustrates a multilayer laser marking film 100 according to an embodiment of the present invention, and specifically, schematically illustrates a cross section thereof.

Referring to FIG. 1, the multilayer laser marking film 100 includes an adhesive layer 10, a colored substrate layer 20, and a colored coating layer 30. For example, the multilayer laser marking film 100 may be formed directly on the adhesive layer 10. A colored substrate layer 20 may be formed on the colored substrate layer 20, and the colored substrate layer 20 may include a multi-layered structure on which the colored coating layer 30 is formed.

In addition, referring to FIG. 1, the multilayer laser marking film 100 includes an uneven pattern X on the surface of the colored coating layer 30. In the present specification, the 'concave-convex pattern' is distinguished from an etching pattern generated by laser marking, and is a configuration that is essentially included in the surface of the colored coating layer before laser marking.

The multi-layer laser marking film 100 may have a background of various patterns through the concave-convex pattern (X), for example, in the form of the concave-convex pattern (X) on the surface of the colored coating layer 30, the character and The logo can be entered to perform various possibilities in terms of design and merchandise.

The multilayer laser marking film is a film which can be etched by a laser to write various information. In the present specification, 'laser marking' means writing information on a film by etching by a laser. Specifically, in the multilayer laser marking film, laser marking may be performed on the colored coating layer.

That is, the multilayer laser marking film has laser marking property, and the 'laser marking property' refers to physical properties in which the colored coating layer is etched by laser irradiation and the etched portion is removed. As such, the laser irradiated portion of the colored coating layer is etched and removed to interact with the colored substrate layer to write various letters, patterns, and the like.

The colored base layer 20 and the colored coating layer 30 are both colored layers, meaning 'colored' indicates that the base layer or coating layer is not transparent and has a color such as white, black, blue, or the like. . Specifically, the colored base layer 20 has a first color, the colored coating layer 30 has a second color, and the first color and the second color are different colors from each other.

As such, when the colored substrate layer and the colored coating layer have different colors from each other, when the colored coating layer is etched by laser marking, the etched portion may exhibit various colors according to the etching depth.

2 schematically illustrates a cross section when laser marking is performed on a multilayer laser marking film 100 according to an embodiment of the present invention.

Referring to FIG. 2A, when all of the colored coating layers 30 are etched by laser marking, only the first color of the colored substrate layer 20 may be visually recognized. In addition, referring to FIG. 2B, when a part of the thickness of the colored coating layer 30 is etched, the colored coating layer 30 remaining without being etched with the first color of the colored base layer 20 is etched. The color in which the second color overlaps may be visually recognized.

The multilayer laser marking film can be written characters or patterns of various colors through the laser marking in this way. For example, the multilayer laser marking film may be used in automobiles, and specifically, may display information about various parts of the vehicle such as tire pressure or fuel type, or may provide unique security information such as chassis number and vehicle identification number. Can be used to indicate.

The multilayer laser marking film needs to prevent forgery or tampering when important information is entered. Specifically, the multilayer laser marking film may have 'self-fragmentability'. "Self-fragmentable" means a physical property that the original shape is broken and cannot be recycled when an attempt is made to detach or remove the multilayer laser marking film after it is attached to the adherend. Since the multilayer laser marking film has self-fragmentation property, it is impossible to arbitrarily change the unique information written therein, and it is possible to secure a property that cannot be forged or modulated.

In addition, the multilayer laser marking film has excellent magnetic crushing property after being applied to the final article, and is evaluated in the physical properties such as adhesive force before being applied to the final article, or during the process of manufacturing the multilayer laser marking film; Alternatively, the manufactured multilayer laser marking film may have physical properties that do not break during distribution, that is, resistance to magnetic fracture and stability. In general, the film having the magnetic crushing property has a problem that the film is torn or broken due to the magnetic crushing property when evaluating physical properties such as adhesion. In particular, in the case of a film having an adhesive layer having a high adhesive force, there is a problem that the measurement of the adhesive force becomes more difficult.

However, the multilayer laser marking film may include a pressure-sensitive adhesive layer having a high adhesion but may not be torn or broken when evaluating physical properties such as adhesion, and at the same time, it is applied to the final article to improve self-fragmentation after a predetermined time has elapsed. It may have an advantage indicating.

The above advantages and properties of the multilayer laser marking film may be implemented through specific compositions and laminated structures of the colored substrate layer, the colored coating layer, and the adhesive layer, as described below.

Specifically, the colored coating layer includes a cured product of the coating composition including a photocurable oligomer, a thermosetting oligomer and a pigment. The coating composition contains a photocurable oligomer and a thermosetting oligomer at the same time, and has a dual curability capable of both thermosetting and photocuring, the cured product of the coating composition is at least one step of photocuring and at least one step of heat It is a dual hardened | cured material by hardening.

Specifically, the photocurable oligomer includes an epoxy (meth) acrylate oligomer, a urethane (meth) acrylate oligomer or a mixed oligomer thereof. That is, the coating composition may include any one of the epoxy (meth) acrylate oligomer and the urethane (meth) acrylate oligomer as a photocurable oligomer, or may include a mixture thereof.

For example, when the photocurable oligomer comprises mixed oligomers thereof, the weight ratio of the epoxy (meth) acrylate oligomer to the urethane (meth) acrylate oligomer may be about 50:50 to about 10:90. . By using these photocurable oligomers by mixing them in the weight ratio in the above range, there is an advantageous advantage in the surface hardness and chemical resistance, and visibility when forming irregularities.

The said epoxy (meth) acrylate oligomer and the urethane (meth) acrylate oligomer are bifunctional to six functional polyfunctional oligomers, respectively. That is, the epoxy (meth) acrylate oligomer and the urethane (meth) acrylate oligomer each have 2 to 6 (meth) acrylate groups as photocurable functional groups in one molecule. As a result, the coating composition may be cured to have an appropriate hardness while maintaining the shape of the uneven pattern well, and may secure a viscosity suitable for forming the uneven pattern.

Further, the epoxy (meth) acrylate oligomer and the urethane (meth) acrylate oligomer each have a weight average molecular weight (Mw) of about 500 g / mol to about 5000 g / mol, for example, about 500 g / mol to about 4000 g / mol. As a result, the coating composition may be cured to have an appropriate hardness while maintaining the shape of the concave-convex pattern during the curing process, and may secure a viscosity suitable for forming the concave-convex pattern.

The epoxy (meth) acrylate oligomer is a (meth) acrylate compound containing an epoxy structural unit in one molecule, and more specifically, a bisphenol A type epoxy (meth) acrylate oligomer and a bisphenol F type epoxy (meth) acrylate Oligomers, phenol novolac epoxy (meth) acrylate oligomers, aliphatic alkyl epoxy (meth) acrylate oligomers, modified epoxy (meth) acrylate oligomers, and combinations thereof.

In addition, the urethane (meth) acrylate oligomer is a (meth) acrylate compound containing a urethane structural unit in one molecule, more specifically, a polyester urethane (meth) acrylate oligomer, polybutadiene urethane (meth) acrylate From oligomers, polyether urethane (meth) acrylate oligomers, caprolactone modified urethane (meth) acrylate oligomers, pentaerythritol tetraacrylate (PETA) conjugated six-functional urethane (meth) acrylate oligomers and combinations thereof It may include the selected one.

In addition, the thermosetting oligomer includes an isocyanate oligomer.

The isocyanate oligomer is an oligomer having at least one isocyanate group in one molecule. Specifically, the isocyanate oligomer may be a bifunctional to six functional polyfunctional oligomer. By having a functional group in the above range, the coating composition may secure an appropriate degree of curing by thermal curing, and as a result, surface durability of the multilayer laser marking film may be improved.

In addition, the isocyanate oligomer may have a weight average molecular weight (Mw) of about 100 g / mol to about 2,000 g / mol, for example, about 150 g / mol to about 1,500 g / mol. As a result, the coating composition may be cured to have an appropriate hardness while maintaining the shape of the concave-convex pattern during the thermosetting process, and may secure a viscosity suitable for forming the concave-convex pattern and applying the printing method.

Specifically, the isocyanate oligomer is a biuret type hexamethylene diisocyanate (HDI) oligomer, isocyanurate type hexamethylene diisocyanate (HDI) oligomer, adduct type hexamethylene Diisocyanate (HDI) oligomer, biuret type isophorone diisocyanate (IPDI) oligomer, isocyanurate type isophorone diisocyanate (IPDI) oligomer, adduct type isophorone di Isocyanate (IPDI) oligomer, adduct type xylene diisocyanate (XDI) oligomer, adduct type 1,4-bis (isocyanatemethyl) cyclohexane (H6XDI) oligomer, adduct type It may include one selected from the group consisting of 1,3-bis (isocyanate methyl) cyclohexane (H6XDI) oligomer and combinations thereof have.

In one embodiment, the isocyanate oligomer is hexamethylene diisocyanate (HDI) oligomer of isocyanurate type, 1,3-bis (isocyanatemethyl) cyclohexane (H6XDI) oligomer of adduct type It may include one selected from the group consisting of adduct type isophorone diisocyanate (IPDI) oligomer and combinations thereof, in this case, excellent light resistance compared to other types of isocyanate oligomers, It is resistant to discoloration, and improves the hardness of the surface, thereby making it easy to form irregularities and secure visibility.

As described above, the coating composition uses a photocurable oligomer and a thermosetting oligomer together, and realizes dual curing performance.

In this case, the weight ratio of the photocurable oligomer to the thermosetting oligomer may be about 75:25 to about 98: 2, for example, about 80:20 to about 98: 2. As a result, the coating composition may obtain a colored coating layer that realizes the desired surface durability through thermal curing and dual curing of photocuring, and the uneven pattern of the colored coating layer surface may be precisely formed.

The coating composition may include a pigment for implementing a color, and the pigment may be variously selected within a range in which the colored base layer and the colored coating layer implement different colors from each other.

For example, the pigment may include one selected from the group consisting of titanium dioxide (TiO ₂ ), carbon black, silicon dioxide (SiO 2), zinc oxide, and combinations thereof.

The coating composition may further include a photoinitiator and a thermosetting catalyst. The photoinitiator is a component that initiates a photocuring reaction, and the thermosetting catalyst may serve to improve the efficiency of the thermosetting reaction.

The photoinitiator is not particularly limited as long as it is a compound capable of initiating a photocuring reaction. For example, a benzophenone-based initiator, an alpha-hydroxyketone initiator, a phenylglyoxylate initiator, a benzyldimethyl-ketal initiator, and an alpha One selected from the group consisting of: amino ketone initiators, monoacylphosphine initiators, bisacrylphosphine initiators, bisacylphosphine initiators, phosphine oxide initiators, metallocene initiators, iodonium salt initiators, and combinations thereof It may include.

In addition, the type of the thermosetting catalyst is not particularly limited, but a tin-based catalyst may be used.

The coating composition may have a total content of the photocurable oligomer and the thermosetting oligomer in an amount of about 80 wt% to about 98 wt%, and the content of the pigment may be about 2 wt% to about 20 wt%. The coating composition may increase the interfacial adhesion between the colored coating layer and the colored substrate layer formed therefrom by including the oligomer and the pigment in the content of the above range, the colored coating layer has a suitable surface properties to precisely mark the desired shape Accurately etchable benefits can be obtained. In addition, when forming the concave-convex pattern on the surface of the colored coating layer can be implemented excellent workability and printability.

When the coating composition comprises a photoinitiator and a thermosetting catalyst, their respective content may be about 1% to about 10% by weight. When the content of each of the photoinitiator and the thermosetting catalyst exceeds the above range, there is a fear of discoloration of the colored coating layer after the final curing, and when used below the above range, the photocuring and thermosetting efficiency may be significantly reduced. There is.

Concave-convex pattern of the colored coating layer can be prepared using a printing method, it can be prepared simultaneously with the coating composition. The coating composition is suitable for coating such a printing method, it is possible to write a fine logo, letters, patterns, etc., it is possible to obtain the advantage that their shape is well maintained in the long term.

The concave-convex pattern includes an embossed pattern or an intaglio pattern, and FIG. 1 illustrates an example in the case of having an intaglio pattern. Referring to FIG. 1, the colored coating layer 30 may have a thickness d of about 1 μm to about 5 μm, and a height h of the uneven pattern may be about 0.1 μm to about 1 μm. . The thickness of the colored coating layer 30 and the height h of the concave-convex pattern satisfy each of the above ranges, so that an appropriate design can be realized without degrading the visibility of the information written by laser marking, and the concave-convex pattern is regular. It can be well formed into a shape.

The height of the uneven pattern and the thickness of the colored coating layer may be formed in the above-described range even when the uneven pattern is embossed.

Referring to FIG. 1, the multilayer laser marking film 100 includes a colored substrate layer 20 under the colored coating layer 30.

The colored substrate layer comprises an electron beam cured product of a base composition comprising a monofunctional (meth) acrylate oligomer, a polyfunctional urethane (meth) acrylate oligomer, a polyfunctional epoxy (meth) acrylate oligomer and a pigment. can do.

Since the colored substrate layer includes an electron beam cured product, it may be advantageous to realize proper magnetic crushing and durability as compared with the case of using other curing means such as thermosetting or photocuring.

Specifically, the monofunctional (meth) acrylate oligomer is an oligomer having one (meth) acrylate group as a functional group in one molecule, and more specifically, may include a (meth) acrylate group at the terminal.

The weight average molecular weight (Mw) of the monofunctional (meth) acrylate oligomer may be about 30,000 to about 50,000, in this case it may be advantageous to reduce the modulus when forming the colored substrate layer, to secure flexibility, after curing The deformation due to shrinkage can be effectively prevented.

In addition, the polyfunctional urethane (meth) acrylate oligomer is a urethane oligomer having two or more (meth) acrylate groups in one molecule, for example, a trifunctional urethane (meth) acrylate oligomer or a six-functional urethane (meth) acryl Late oligomers.

In one embodiment, the polyfunctional urethane (meth) acrylate oligomer may include a trifunctional urethane (meth) acrylate oligomer and a six-functional urethane (meth) acrylate oligomer together, in this case, the colored base layer It can be advantageous in terms of enhancing rigidity and surface hardening, and by strengthening the tension of the colored substrate layer, effectively securing the resistance to magnetic fracture during process, distribution and physical data evaluation, while being applied to the final article and at a predetermined time After this elapses, the characteristic which shows the outstanding magnetic fracture property can be implement | achieved effectively.

In this case, the trifunctional urethane (meth) acrylate oligomer may be an aliphatic urethane (meth) acrylate oligomer, and through such chemical structure, the stiffness and tension of the colored substrate layer may be strengthened to process, distribution, and physical property data. It may be advantageous to impart stability to magnetic fracture during the evaluation.

In addition, the six-functional urethane (meth) acrylate oligomer may be an aliphatic urethane (meth) acrylate oligomer, thereby securing fast curing properties to increase the surface cure degree of the colored substrate layer to impart a self-crushing function It may be advantageous to:

The polyfunctional urethane (meth) acrylate oligomer may have a weight average molecular weight (Mw) of about 2,000 to about 5,000, in this case to ensure the final required magnetic crushing performance, while at the same time resistance to magnetic crushing for the required time It may be advantageous to secure.

In addition, the multifunctional epoxy (meth) acrylate oligomer is an epoxy oligomer having two or more (meth) acrylate groups in one molecule, and may include, for example, a bifunctional epoxy (meth) acrylate oligomer. When the polyfunctional epoxy (meth) acrylate oligomer comprises a bifunctional epoxy (meth) acrylate oligomer to increase the hardness of the substrate while giving the flexibility of the substrate to secure the effect of reducing the curling phenomenon due to shrinkage after curing May be more advantageous to

In addition, the bifunctional epoxy (meth) acrylate oligomer may be advantageous to simultaneously give rise to substrate strength and lower substrate shrinkage effect after curing by using those having a bisphenol A (bisphenol A) structure.

The multifunctional epoxy (meth) acrylate oligomer may have a weight average molecular weight (Mw) of about 500 to about 1,500, in which case it may be advantageous to secure the substrate flexibility effect.

The substrate composition can control the modulus of the colored substrate layer by controlling the components contained therein in an appropriate amount, thereby effectively preventing the problem of breakage or tearing while measuring the adhesion of the multilayer laser marking film, and at the same time Improved magnetic crushing property may be achieved when a predetermined time elapses after the multilayer laser marking film is applied to the final article.

Specifically, the base composition includes about 5% to about 20% by weight of the monofunctional (meth) acrylate oligomer and about 10% to about 35% by weight of the polyfunctional urethane (meth) acrylate oligomer. And about 5 wt% to about 30 wt% of the multifunctional epoxy (meth) acrylate oligomer, and about 45 wt% to about 55 wt% of the pigment.

The base composition may include a component in the content of the above range to ensure self-fragmentation to implement a forgery and tamper resistant function, and at the same time the multilayer laser marking film comprising a colored substrate layer prepared therefrom is such as adhesion When evaluating physical properties, it is possible to maximize the property of not tearing or breaking.

The base composition may implement a clear color by including a pigment in the content of the above range. In general, when the content of the pigment is increased, there is a problem in that the viscosity is excessively increased or the processability is deteriorated, but the base composition is required by including the oligomers of the kind and content as described above despite the relatively high content of the pigment. It is possible to secure both self-fragmentability and workability.

The multilayer laser marking film is applied to an article relating to information contained through laser marking, and includes an adhesive layer to adhere to the article. The multilayer laser marking film may exhibit high adhesion to an article finally applied through the adhesive layer, and also include the adhesive layer and the colored base layer together, thereby breaking and tearing even when measuring the adhesion of the film having high adhesion. Can be effectively prevented. Furthermore, when a predetermined time has elapsed after being applied to the final article through the adhesive layer, it may exhibit improved magnetic crushing property.

Specifically, the adhesive layer may have an adhesive force of about 1400 gf / cm or more, for example, about 1400 gf / cm to about 4000 gf / cm. The multilayer laser marking film may include a pressure-sensitive adhesive layer exhibiting adhesion in the above range, so that the pressure-sensitive adhesive layer and the colored substrate layer may be included together, so that the multilayer laser marking film may be measured without breaking or tearing when measuring physical properties of the adhesive force. In addition, the multilayer laser marking film can improve long term adhesion when applied to the final article through an adhesive layer exhibiting adhesion in the above range. The multilayer laser marking film has various uses, for example, may be utilized as a label attached to an automobile, and in this case, the adherend may be a metal paint plate for automobiles, and exhibits adhesion in the above range. Layers can ensure long term adhesion to it.

The adhesive layer may be formed from an adhesive composition including a thermosetting acrylic resin and a curing agent, and may specifically include a cured product of the adhesive composition.

The thermosetting acrylic resin is not particularly limited as long as it can implement the adhesive strength in the above-described range, for example, may be a copolymer of ethylhexyl acrylate (EHA), methyl acrylate (MA) and acrylic acid (AA) Thus, the pressure-sensitive adhesive layer can excellently implement the effect of improving the adhesion and heat resistance to the colored substrate layer.

The thermosetting acrylic resin may have a weight average molecular weight (Mw) of about 100,000 to about 10 million, for example, about 500,000 to about 5 million. When the weight average molecular weight (Mw) of the resin satisfies the above range, the adhesive layer may exhibit high adhesion, and may easily secure adhesion to the colored substrate layer, and may be advantageous in terms of securing heat resistance.

The adhesive composition may include a curing agent together with the thermosetting acrylic resin, and the curing agent may impart improved adhesion to the multilayer laser marking film by allowing the adhesive layer including the cured product of the adhesive composition to have an appropriate gel content. In addition, the multilayer laser marking film may have a required level of magnetic fracture.

The curing agent may include one selected from the group consisting of aziridine-based curing agents, peroxide-based curing agents, isocyanate-based curing agents, and combinations thereof. For example, the curing agent may include an aziridine-based curing agent, in this case, to interact with the thermosetting acrylic resin to implement the rate of increase of the heat resistance, chemical resistance, adhesion performance according to the adhesion time by excellent curing efficiency, etc. May be more advantageous to

The adhesive composition may include about 90% to about 99.999% by weight of the thermosetting acrylic resin, and about 0.001% to about 10% by weight of the curing agent. By using the resin and the curing agent in the content of the above range, the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition may have an appropriate gel content, and at the same time it is possible to secure the adhesion to the colored substrate layer and high adhesion to the final product. Furthermore, improved long term adhesion retention performance can be imparted to the multilayer laser marking film.

3 schematically illustrates a cross section of a multilayer laser marking film 100 ′ according to another embodiment of the invention. Referring to FIG. 3, the multilayer laser marking film 100 ′ may further include a release layer 40 on one surface of the outermost portion.

As shown in FIG. 3A, the release layer 40 may be formed only on one surface of the adhesive layer 10, and as shown in FIG. 3B, one surface of the adhesive layer 10 and the colored coating layer ( 30 may be formed together.

The release layer 40 is a layer removed when the multilayer laser marking film is applied to the final article. The release layer 40 formed on one surface of the colored coating layer 30 may be removed before laser marking, or laser marking. It may then be removed. When the release layer 40 is removed after laser marking, the release layer 40 may be formed of a material having transparency to the laser.

The multi-layer laser marking film is designed to properly design the thickness of the layer to ensure the characteristics of easy laser marking, to realize the magnetic crushing properties, and despite the high adhesion to secure the characteristics of no breakage or tearing when measuring adhesion Can be.

For example, the colored substrate layer may have a thickness of about 60 μm to about 150 μm. Since the thickness of the colored substrate layer satisfies the above range, the multilayer laser marking film may effectively prevent breakage or tearing during adhesive force measurement or manufacturing process while ensuring self-fragmentability.

In addition, the adhesive layer may have a thickness of about 10 μm to about 50 μm. As the thickness of the adhesive layer satisfies the above range, it is possible to implement adhesiveness at a level capable of securing physical properties capable of measuring adhesion without breakage or tearing, and can be applied to a final article to implement excellent long-term adhesion retention performance. .

As described above, the multilayer laser marking film includes the colored substrate layer, the colored coating layer, and the adhesive layer, and by properly designing the components and thickness of each layer, it is possible to secure physical properties capable of measuring adhesion without breakage or tearing. At the same time, it is possible to realize improved self-fragmentation and adhesion retention performance after being applied to the final article.

In another embodiment of the present invention, a method of manufacturing the multilayer laser marking film is provided.

The method of manufacturing the multilayer laser marking film may include applying a substrate composition on one release layer and stacking another release layer on the release layer; Curing the substrate composition to prepare a laminate in which a colored substrate layer having a first color is disposed between two release layers; After removing one release layer from the laminate, a coating composition including a photocurable oligomer, a thermosetting oligomer and a pigment is applied to one surface of the colored substrate layer, in a printing manner to form an uneven pattern on the surface of the coating composition. Applying; Forming a colored coating layer having a second color different from the first color by first and second photocuring the coating composition having the uneven pattern formed thereon; And forming an adhesive layer on the back surface of the colored substrate layer after removing the other release layer from the laminate.

The multi-layer laser marking film manufactured by the manufacturing method may include fine and various characters, patterns, etc. through its uneven pattern on its surface, and may be precisely processed by laser marking, and may not be damaged when evaluating physical properties. Even when applied to a real product, it shows the crushability against forgery and tampering attempts, and has the advantage of realizing excellent security performance.

4 schematically illustrates a method of manufacturing a multilayer laser marking film according to an embodiment of the present invention.

Referring to FIG. 4, in the method of manufacturing the multilayer laser marking film, applying the base composition A on one release film 50 and laminating another release film 50 thereon ( S100). The matter regarding the said base composition is as mentioned above.

The method of applying the substrate composition (A) on the one release film 50 is not particularly limited, for example, spin coating method, bar coating method, comma coating method, slot die coating method, A gravure coating method, a roll coating method, or the like can be used.

Subsequently, the manufacturing method includes preparing a laminate in which the colored substrate layer 20 having the first color is disposed between the two release films 50 by curing the substrate composition (A) (S200). The substrate composition (A) may be cured by the method of electron beam curing as described above.

As described above, the method of manufacturing the multilayer laser marking film preferentially forms a laminate having a structure in which a colored substrate layer is interposed between two release films, thereby improving the interfacial adhesion between the layers in the process of manufacturing the colored coating layer and the adhesive layer. It is possible to improve and to realize the advantage of reducing the process failure rate. In addition, the magnetic crushing performance of the multilayer laser marking film can be improved.

Subsequently, the manufacturing method removes one release film 50 from the laminate, and then applies a coating composition (B) including a photocurable oligomer, a thermosetting oligomer and a pigment to one surface of the colored substrate layer 20. It includes a step (S300) of applying a printing method so that the concave-convex pattern (X) is formed on the surface of the coating composition.

The coating composition (B) includes a photocurable oligomer, a thermosetting oligomer and a pigment, all of which are the same as described above.

The uneven pattern (X) may be prepared using a printing method as described above, it may be prepared at the same time with the coating composition (B). The coating composition is suitable for producing the colored coating layer 30 containing the concave-convex pattern (X) in this way, thereby through the concave-convex pattern (X), essentially contained in the colored coating layer 30 before laser marking. It is possible to efficiently produce finely shaped logos, letters, designs and the like, and to obtain the advantage that their shapes are well maintained during the use of laser marking or multilayer laser marking film.

More specifically, the printing method is not particularly limited, but may use a flexo printing method, a gravure printing method, or an inkjet printing method.

In this case, the viscosity of the coating composition (B) may be about 5cps to about 50cps at room temperature of about 20 ℃ to about 30 ℃. The viscosity of the coating composition (B) may be uniformly applied by satisfying the above range, and may exhibit excellent processability when subsequently forming an uneven pattern by a printing method.

Subsequently, the manufacturing method includes forming a colored coating layer 30 having a second color different from the first color by performing primary thermal curing (S400) and secondary photocuring (S500) on the uneven patterned coating composition. It includes.

The coating composition (B) may be temporarily cured by applying heat primarily, and may be additionally hardened by light irradiation.

In this case, the first thermal curing may be performed for about 5 minutes to about 30 minutes at a temperature of about 100 ℃ to about 150 ℃. The coating composition (B) may be temporarily cured to an appropriate hardness by performing primary heat curing at a temperature in the above range. If the first thermal curing is performed at a temperature and time lower than the above-mentioned range, there is a problem that the coating layer is desorbed or erased due to insufficient curing. There is a problem that (crack) occurs.

In addition, secondary photocuring after the primary thermal curing may be further cured by irradiating light energy of 300mJ to 500mJ with a fusion mercury lamp. When the secondary photocuring is performed by the light energy lower than the above range, there is a problem that the chemical resistance and adhesion due to the uncured coating layer is not secured, and when the secondary photocuring is performed with the light energy exceeding the above range, There is a problem that cracks in the coating layer.

The method of manufacturing the multilayer laser marking film may additionally perform tertiary thermal curing after the secondary photocuring. As such, when additional tertiary thermal curing is performed, the uneven pattern formed on the surface of the colored coating layer may be more firmly formed, whereby an etching shape may be precisely realized at a later laser marking, and the multilayer laser marking film may be excellent. It can exhibit long term durability.

When performing the third heat curing, it may be performed for about 72 hours to about 24 hours at a temperature of about 40 ℃ to about 80 ℃.

The method of manufacturing the multilayer laser marking film may then include forming an adhesive layer 10 on the other side of the colored substrate layer, that is, the other side of the colored substrate layer, which is then exposed after removing the other release film 50 from the laminate ( S600).

Specifically, the pressure-sensitive adhesive layer 10 may include a cured product of the pressure-sensitive adhesive composition containing a thermosetting acrylic resin and a curing agent, the details of which are as described above.

Through the method of manufacturing the multilayer laser marking film, the multilayer laser marking film may be manufactured, and the thickness of each layer may be manufactured to satisfy the above-mentioned range.

In addition, if necessary, the method of manufacturing the multilayer laser marking film may further include forming a release layer 40 on one side or both sides of the outermost part, and the details of the release layer 40 are as described above. .

The following presents specific embodiments of the present invention. However, the embodiments described below are merely for illustrating or explaining the present invention in detail, and thus the present invention is not limited thereto.

< Example  And Comparative example >

Example  1-4

5% by weight of a monofunctional urethane acrylate oligomer on one surface of a polyethylene terephthalate (PET) release film; 15% by weight of trifunctional urethane acrylate oligomer; 12 wt% of the 6-functional urethane acrylate oligomer; 20% by weight bifunctional epoxy acrylate oligomer; And 48 wt% of a titanium dioxide (TiO ₂ ) pigment was applied, and the same PET release film was laminated thereon. Subsequently, a laminate having a colored substrate layer having a thickness of 100 μm was interposed between the two release films by curing the substrate composition through electron beam curing.

Subsequently, the coating composition including each of the photocurable oligomer, thermosetting oligomer, carbon black, photoinitiator (Irgacure 184) and tin catalyst (DBTL) in the amounts shown in Table 1 was diluted with solvents (MEK and MIBK). It was prepared to have a viscosity of 20 cps. Subsequently, one release film of the laminate is peeled off, and the coating composition is applied to one surface of the colored substrate layer on which the release film is peeled off by a gravure printing method, and the uneven pattern having a height of 1 μm on the surface thereof. It was applied to form

Subsequently, the coating composition was first thermally cured at a temperature of 100 ° C. for 5 minutes, and a secondary coating was performed by irradiating 300 mJ of light energy with a Fusion mercury lamp to prepare a colored coating layer having a thickness of 5 μm.

 Subsequently, the coating composition was thermally cured for 3 hours at a temperature of 60 ° C.

Subsequently, another release film of the laminate was peeled off, and 99 wt% of a thermosetting acrylic resin having a weight average molecular weight (Mw) of 500,000 to 5 million and 1 wt% of an aziridine curing agent on the back surface of the colored coating layer thus revealed. After applying the pressure-sensitive adhesive composition containing a thermosetting for 5 minutes at 120 ℃ to prepare a pressure-sensitive adhesive layer of 25㎛ thickness.

As a result, a multilayer laser marking film in which a colored coating layer, a colored substrate layer, and an adhesive layer were laminated was manufactured.

Comparative example  1-3

A multilayer laser marking film was prepared in the same manner as in the above examples, except that each of the coating compositions was used in the ingredients and contents shown in Table 1 below.

Coating Composition [% by weight] Photocurable
Oligomer Thermosetting
Oligomer Carbon
black ore
Initiator Tin
catalyst Kinds content Kinds content content content content room
city
Yes One Bisphenol A system
2-functional EAO 33 Trifunctional isocyanurate type
HDI oligomer 14 9 6 5 Aliphatic
Trifunctional UAO 33 2 Bisphenol A system
2-functional EAO 10 6-functional isocyanurate type
HDI oligomer 2 9 6 6 Aliphatic
Trifunctional UAO 73 3 Bisphenol A system
2-functional EAO 32 Trifunctional H6XDI Oligomer 15 9 6 6 Aliphatic
Trifunctional UAO 32 4 Bisphenol A system
2-functional EAO 10 Trifunctional isocyanurate type
HDI oligomer 10 9 6 6 Aliphatic
Trifunctional UAO 59 ratio
School
Yes One Bisphenol A system
2-functional EAO 40 - 9 6 5 Aliphatic
Trifunctional UAO 40 2 Bisphenol A system
2-functional EAO 10 Novolac epoxy type oligomer 10 9 6 6 Aliphatic
Trifunctional UAO 59 3 Bisphenol A system
2-functional EAO 4 Trifunctional isocyanurate type
HDI oligomer 14 9 6 6 Aliphatic
Trifunctional UAO 66

* UAO: urethane acrylate oligomer

* EAO: epoxy acrylate oligomer

* HDI: hexamethylene diisocyanate

* H6XDI: 1,4-bis (isocyanatemethyl) cyclohexane

<Evaluation>

Experimental Example  1: evaluation of chemical resistance

For each of the multi-layered laser films of Examples 1-4 and Comparative Examples 1-3, after attaching each adhesive layer to be in contact with an automobile paint plate made of stainless steel, the surface of the colored coating layer was After immersion in gasoline, brake oil, engine oil and antifreeze for 2 hours, respectively, rubbed five times with a cloth, and visually observed the surface to evaluate the chemical resistance, the results are shown in Table 2 below.

Specifically, the case where there is no discoloration, dropping, or swelling of the coating layer even after 2 hours immersion for all the solutions is described as 'OK', and at least one of discoloration, dropping, or swelling for at least one of the above solutions is described. The case where one phenomenon occurs is described as 'NG'.

Experimental Example  2: measurement of different adhesion force changes over time

For each of the multi-layered laser marking films of Examples 1-4 and Comparative Examples 1-3, each adhesive layer was attached to contact an automotive paint plate made of stainless steel, and then prescribed as shown in Table 3 below. The adhesion force after time passed was measured. Adhesion was measured by applying a load in the direction of 90 degrees at a rate of 300 mm / min at room temperature using a tensile tester based on the method based on ASTM D3330. In addition, it was observed whether or not each multilayer laser marking film had self-fragmentation after a predetermined time had elapsed since the adhesion.

Experimental Example  3: evaluation of wear resistance

Each of the multilayer laser marking films of Examples 1-4 and Comparative Examples 1-3 was attached to a circular plate and after 24 hours, abrasion resistance test was performed using a Taber tester. The horse wheel cap was used as CS-10, the load was 500gf, and the rotation speed was 70 times / min. The rotation speed was measured when the laser etching pattern disappeared. The results are as described in Table 2 below.

Chemical resistance Adhesion over time [gf / cm] Wear resistance Irregularities formation 1 hour later 24 hours later 48 hours later 3 days later Example 1 OK 1210 2520 3020 Shred 600 OK Example 2 OK 1180 2600 3100 Shred 500 OK Example 3 OK 1200 2400 3060 Shred 550 OK Example 4 OK 1240 2610 3180 Shred 600 OK Comparative Example 1 OK 1190 2420 3100 Shred 450 NG Comparative Example 2 Not measurable due to uncured color coating layer NG Comparative Example 3 Not measurable due to uncured color coating layer NG

When referring to Table 1 and Table 2, the multilayer laser marking film of Examples 1 to 4 according to an embodiment of the present invention is formed with a concave-convex pattern on the surface of the colored coating layer, excellent chemical resistance, and at the same time It can be seen that the crushability is also excellent.

In the case of Comparative Example 1, but the crushing property is implemented to a certain level, wear resistance is inferior to Examples 1 to 4, it can be seen that there is a problem that the irregularities are not formed firmly.

In addition, in Comparative Examples 2 to 3, the degree of curing of the colored coating layer was not sufficiently secured, so that the uneven structure was not formed, and further, it was found that the chemical resistance, the wear resistance, and the fracture resistance were not secured at all.

100: multilayer laser marking film
10: adhesive layer
20: colored base material layer
30: colored coating layer
40: release layer
50: release film
A: base material composition
B: coating composition
X: uneven pattern

Claims (21)

Adhesive layer; A colored base layer having a first color; And a colored coating layer having a second color, wherein the first color and the second color are different colors from each other,
The colored coating layer comprises a cured product of the coating composition comprising a photocurable oligomer, a thermosetting oligomer and a pigment,
The photocurable oligomer includes an epoxy (meth) acrylate oligomer, a urethane (meth) acrylate oligomer or a mixed oligomer thereof,
The thermosetting oligomer includes an isocyanate oligomer,
The colored coating layer comprises a concave-convex pattern on the surface,
The colored substrate layer comprises an electron beam cured product of a base composition comprising a monofunctional (meth) acrylate oligomer, a polyfunctional urethane (meth) acrylate oligomer, a polyfunctional epoxy (meth) acrylate oligomer and a pigment. doing
Multilayer Laser Marking Film.
The method of claim 1,
The colored coating layer is etched by laser irradiation, and the laser marking property that the etched portion is removed
Multilayer Laser Marking Film.
The method of claim 1,
The epoxy (meth) acrylate oligomer and the urethane (meth) acrylate oligomer are each bifunctional to six functional
Multilayer Laser Marking Film.
The method of claim 1,
The epoxy (meth) acrylate oligomer and the urethane (meth) acrylate oligomer each have a weight average molecular weight (Mw) of 500 g / mol to 5,000 g / mol
Multilayer Laser Marking Film.
The method of claim 1,
The epoxy (meth) acrylate oligomers include bisphenol A epoxy (meth) acrylate oligomers, bisphenol F epoxy (meth) acrylate oligomers, phenol novolac epoxy (meth) acrylate oligomers, and aliphatic alkyl epoxy (meth) acrylates. Comprising one selected from the group consisting of oligomers, modified epoxy (meth) acrylate oligomers, and combinations thereof
Multilayer Laser Marking Film.
The method of claim 1,
The urethane (meth) acrylate oligomer may be polyester urethane (meth) acrylate oligomer, polybutadiene urethane (meth) acrylate oligomer, polyether urethane (meth) acrylate oligomer, caprolactone modified urethane (meth) acrylate oligomer, Pentaerythritol tetraacrylate (PETA) utilization 6 functional urethane (meth) acrylate oligomer and a combination comprising one selected from the group consisting of
Multilayer Laser Marking Film.
The method of claim 1,
The mixed oligomer is a mixture of epoxy (meth) acrylate oligomer to urethane (meth) acrylate oligomer in a weight ratio of 50:50 to 10:90
Multilayer Laser Marking Film.
The method of claim 1,
The isocyanate oligomer has a weight average molecular weight (Mw) of 100 g / mol to 2,000 g / mol
Multilayer Laser Marking Film.
The method of claim 1,
The isocyanate oligomer is a biuret type hexamethylene diisocyanate (HDI) oligomer, isocyanurate type hexamethylene diisocyanate (HDI) oligomer, adduct type hexamethylene diisocyanate ( HDI) oligomer, biuret type isophorone diisocyanate (IPDI) oligomer, isocyanurate type isophorone diisocyanate (IPDI) oligomer, adduct type isophorone diisocyanate (IPDI) ) Oligomer, adduct type xylene diisocyanate (XDI) oligomer, adduct type 1,4-bis (isocyanatemethyl) cyclohexane (H6XDI) oligomer, adduct type 1, 3-bis (isocyanatemethyl) cyclohexane (H6XDI) oligomer and combinations thereof
Multilayer Laser Marking Film.
The method of claim 1,
The coating composition has a weight ratio of the photocurable oligomer to the thermosetting oligomer is from 75:25 to 98: 2.
Multilayer Laser Marking Film.
The method of claim 1,
The colored coating layer has a thickness of 1 μm to 5 μm,
The height of the uneven pattern is 0.1㎛ to 1㎛
Multilayer Laser Marking Film.
delete The method of claim 1,
The polyfunctional urethane (meth) acrylate oligomer comprises a trifunctional urethane (meth) acrylate oligomer or a six functional urethane (meth) acrylate oligomer
Multilayer Laser Marking Film.
The method of claim 1,
The polyfunctional epoxy (meth) acrylate oligomer comprises a bifunctional epoxy (meth) acrylate oligomer
Multilayer Laser Marking Film.
The method of claim 1,
The base composition is 5 to 20% by weight of the monofunctional (meth) acrylate oligomer; 10 wt% to 35 wt% of the multifunctional urethane (meth) acrylate oligomer; 5 wt% to 30 wt% of the multifunctional epoxy (meth) acrylate oligomer; And 45 wt% to 55 wt% of the pigment.
Multilayer Laser Marking Film.
The method of claim 1,
The adhesive layer has an adhesion force of 1400 gf / cm or more to the metal substrate
Multilayer Laser Marking Film.
The method of claim 1,
The pressure-sensitive adhesive layer comprises a cured product of the pressure-sensitive adhesive composition containing a thermosetting acrylic resin and a curing agent.
Multilayer Laser Marking Film.
The method of claim 17,
The adhesive composition is 90% by weight to 99.999% by weight of the thermosetting acrylic resin; And 0.001% to 10% by weight of the curing agent.
Multilayer Laser Marking Film.
Applying a base composition on one release film, and laminating another release film thereon;
Curing the substrate composition to prepare a laminate having a colored substrate layer having a first color disposed between two release films;
After removing one release film from the laminate, a coating composition including a photocurable oligomer, a thermosetting oligomer and a pigment is applied to one surface of the colored substrate layer, and a printing method is performed such that an uneven pattern is formed on the surface of the coating composition. Applying;
Forming a colored coating layer having a second color different from the first color by first and second photocuring the coating composition having the uneven pattern formed thereon; And
Removing the other release film from the laminate and forming a pressure-sensitive adhesive layer on the back surface of the colored substrate layer;
The method for producing a multilayer laser marking film according to any one of claims 1 to 11 and 13 to 18.
The method of claim 19,
After the secondary photocuring to further perform the third thermal curing
Method for producing a multilayer laser marking film.
The method of claim 19,
The printing method may be a flexo printing method, a gravure printing method, or an inkjet printing method.
Method for producing a multilayer laser marking film.

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